title: Structure and other molecular properties of actinide trichlorides AnCl3 (An = Th-Cm).
abstract: The ground-state molecular properties of the trichlorides of light actinides (An = Th-Cm) have been predicted by state-of-the-art quantum chemical calculations. The ground electronic states have been determined by multireference calculations at the CASPT2 level including both scalar and spin-orbit relativistic effects. These studies supported the expected single-configuration character of ThCl3 and CmCl3 with their well-defined 6dσ/7s hybrid and 5f(7) configurations, respectively. In contrast, the intermediate actinides (PaCl3-AmCl3) with partly filled 5f shells have numerous very low-lying excited states and consequently a mixed character of the spin-orbit ground states. Apart from the planar ThCl3 the ground-state molecular geometries proved to be pyramidal with C(3v) symmetry. The gradually decreasing An-Cl bond distances reveal the actinide contraction known for the atomic and ionic radii of these actinide atoms. Other ground-state molecular properties as vibrational frequencies and natural charges have been obtained by density functional theory calculations using the B3LYP exchange-correlation functional in conjunction with small-core relativistic energy-consistent pseudopotentials for the actinides.
authors.affiliation: European Commission, Joint Research Centre, Institute for Transuranium Elements , P.O. Box 2340, 76125 Karlsruhe, Germany.
authors.forename: Attila
authors.initials: A
authors.lastname: Kovács
authors.forename: Rudy J M
authors.initials: RJ
authors.lastname: Konings
authors.forename: Zoltán
authors.initials: Z
authors.lastname: Varga
authors.forename: Dénes
authors.initials: D
authors.lastname: Szieberth